Polynuclear rhodium(II) compounds with phosphino-phenoxide ligands

Dunbar, Kim R.; Matonic, John H.; Saharan, Vijay P.

doi:10.1021/ic00079a007

Cited by 36 publications

(3 citation statements)

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“…The specific DAB ligand initially designed in this exercise is shown as L where the two additional coordination sites are ether oxygens capable of weak but significant binding to metal ions. Studies by Dunbar on complexes of the functionalized phosphine P(2,4,6-C 6 H 2 (OMe) 3 ) 3 demonstrate the importance and versatility of coordination by the ortho methoxy ether substituents in stabilizing octahedral Rh(II) and Pd(II) ions. − …”

Section: Introductionmentioning

confidence: 99%

“…Studies by Dunbar on complexes of the functionalized phosphine P(2,4,6-C 6 H 2 (OMe) 3 ) 3 demonstrate the importance and versatility of coordination by the ortho methoxy ether substituents in stabilizing octahedral Rh(II) and Pd(II) ions. [25][26][27] A second aspect in the design of L is that, for squareplanar complexes similar to Brookhart's active catalysts, 1-9 two possible isomers for the ML moiety would existsone having C 2 symmetry and the other with mirror symmetryswith possible stereochemical consequences in reactions promoted or catalyzed by it. Spe-cifically, for the ML moiety of C 2 symmetry, diastereomeric interactions between the catalyst complex and prochiral substrates would exist.…”

Section: Introductionmentioning

confidence: 99%

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Unsymmetrical 1,4-Diazabutadiene Complexes of Platinum(II)

1997

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The new unsymmetrical 1,4-diazabutadiene ligand glyoxal bis(2-(methoxymethyl)-4,6-di-tert-butylphenyl)diimine (L) and its reduced analog (LH 4 ) were synthesized. The reactions of both ligands with bis(benzonitrile) complexes of palladium and platinum, MCl2(PhCN)2, were investigated. Two isomers of formula MCl2 L were isolated from the reaction of L with MCl2(PhCN)2 (1a and 1b for Pd, 2a and 2b for Pt), while only a single product, MCl2(LH 4 ), formed in the reaction with LH 4 (3 for M = Pd, 4 for M = Pt). All new compounds were characterized by elemental analyses and IR and NMR spectroscopies. The molecular structures for L, LH 4 , 2b, 3, and 4 were determined by single-crystal X-ray diffraction. The metal complexes exhibit distorted square-planar geometry. The aryl groups of the L and LH 4 ligands lie out of the coordination plane in a manner that blocks potential axial ligation sites. Ligand L crystallizes in the triclinic space group P1̄ with a = 5.760(1) Å, b = 9.383(2) Å, c = 14.954(3) Å, α = 89.38(2)°, β = 79.67(2)°, γ = 88.14(2)°, and Z = 1. The reduced ligand LH 4 crystallizes in the monoclinic space group P21 with a = 5.9758(1) Å, b = 17.4272(2) Å, c = 15.6222(1) Å, β = 99.063(1)°, and Z = 2. Complex 2b crystallizes in the monoclinic space group P21/c with a = 16.9599(2) Å, b = 18.4985(2) Å, c = 12.4976(0) Å, β = 100.945(0)°, and Z = 4. Complex 3 crystallizes in the monoclinic space group C2/c with a = 36.1506(8) Å, b = 8.0994 (2) Å, c = 15.5671(1) Å, β = 113.988(1)°, and Z = 4. Complex 4 crystallizes in the monoclinic space group C2/c with a = 36.0649(3) Å, b = 8.1787(2) Å, c = 15.7585(3) Å, β = 112.610(1)°, and Z = 4.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Unsymmetrical 1,4-Diazabutadiene Complexes of Platinum(II)

1997

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“…The torsion angles of C(1), C(6), C(7), N(1), and C(17), C(12), C(11), N(2) are −10.1(12), and −16.6(9)°, respectively. The Rh−P, Rh−N, Rh−O, and Rh−C distances all are in the normal range for rhodium complexes …”

Section: Resultsmentioning

confidence: 97%

Dinuclear Palladium, Nickel, and Rhodium Complexes Based on 1,3-Bis[(2-(diphenylphosphino)benzylidene)amino]propan-2-ol

et al. 1998

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Nickel Chelate Complexes of 2-Alkylphenylphosphanylphenolates: Synthesis, Structural Investigation and Use in Ethylene Polymerization

Heinicke¹,

Koesling

Brüll

et al. 2000

Eur. J. Inorg. Chem.

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2‐Diphenylphosphanyl‐ and 2‐alkylphenylphosphanyl‐4‐methylphenols 1 or their silyl ethers 2 and equimolar amounts of nickelocene react in benzene preferably to give orange‐brown diamagnetic cyclopentadienylnickel chelate complexes [η‐CpNi(P∩O)] (3). Addition of a second equivalent of 1 or 2 affords (RR) and (SS) diastereoisomers of cis‐bis(P∩O‐chelates) 4a–c (R = Ph, Me, iPr) or the unsymmetrical cis‐bis(P∩O‐chelate) 5, whereas with bulkier substituted derivatives 1d or 2d (R = tBu) the second step is hindered or retarded. The reactivity of 1d remains high towards nickel salts in polar solvents, but in contrast to 1a–c, yielding 4, a sparingly soluble green trans‐bis(P–O‐chelate) nickel complex 6d is formed. Complexes formed in situ from 1 or 2 and Ni(COD)2 in toluene catalyze the polymerization of ethylene. The cyclopentadienyl (P∩O) complexes 3, however, are too stable to be active in this process. The crystal and molecular structure of 3c and 4c are described.

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Polynuclear rhodium(II) compounds with phosphino-phenoxide ligands

Cited by 36 publications

References 1 publication

Unsymmetrical 1,4-Diazabutadiene Complexes of Platinum(II)

Unsymmetrical 1,4-Diazabutadiene Complexes of Platinum(II)

Dinuclear Palladium, Nickel, and Rhodium Complexes Based on 1,3-Bis[(2-(diphenylphosphino)benzylidene)amino]propan-2-ol

Nickel Chelate Complexes of 2-Alkylphenylphosphanylphenolates: Synthesis, Structural Investigation and Use in Ethylene Polymerization

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